Cornelissen Gerard, Gustafsson Orjan, Bucheli Thomas D, Jonker Michiel T O, Koelmans Albert A, van Noort Paul C M
Department of Applied Environmental Sciences (ITM), Stockholm University, 10691 Stockholm, Sweden.
Environ Sci Technol. 2005 Sep 15;39(18):6881-95. doi: 10.1021/es050191b.
Evidence is accumulating that sorption of organic chemicals to soils and sediments can be described by "dual-mode sorption": absorption in amorphous organic matter (AOM) and adsorption to carbonaceous materials such as black carbon (BC), coal, and kerogen, collectively termed "carbonaceous geosorbents" (CG). Median BC contents as a fraction of total organic carbon are 9% for sediments (number of sediments, n approximately 300) and 4% for soils (n = 90). Adsorption of organic compounds to CG is nonlinear and generally exceeds absorption in AOM by a factor of 10-100. Sorption to CG is particularly extensive for organic compounds that can attain a more planar molecular configuration. The CG adsorption domain probably consists of surface sites and nanopores. In this review it is shown that nonlinear sorption to CG can completely dominate total sorption at low aqueous concentrations (<10(-6) of maximum solid solubility). Therefore, the presence of CG can explain (i) sorption to soils and sediments being up to 2 orders of magnitude higher than expected on the basis of sorption to AOM only (i.e., "AOM equilibrium partitioning"), (ii) low and variable biota to sediment accumulation factors, and (iii) limited potential for microbial degradation. On the basis of these consequences of sorption to CG, it is advocated that the use of generic organic carbon-water distribution coefficients in the risk assessment of organic compounds is not warranted and that bioremediation endpoints could be evaluated on the basis of freely dissolved concentrations instead of total concentrations in sediment/soil.
越来越多的证据表明,有机化学品在土壤和沉积物中的吸附作用可用“双模式吸附”来描述:在无定形有机物(AOM)中的吸收以及对碳质材料(如黑碳(BC)、煤和干酪根)的吸附,这些碳质材料统称为“碳质地质吸附剂”(CG)。沉积物(沉积物数量,n约为300)中BC含量占总有机碳的中位数为9%,土壤(n = 90)中为4%。有机化合物在CG上的吸附是非线性的,通常比在AOM中的吸收高10至100倍。对于能够形成更平面分子构型的有机化合物,在CG上的吸附尤为显著。CG的吸附域可能由表面位点和纳米孔组成。在本综述中表明,在低水浓度(<最大固体溶解度的10^(-6))下,对CG的非线性吸附可完全主导总吸附。因此,CG的存在可以解释:(i)在土壤和沉积物中的吸附比仅基于对AOM的吸附(即“AOM平衡分配”)预期的高2个数量级;(ii)生物群与沉积物积累因子低且变化不定;(iii)微生物降解潜力有限。基于对CG吸附的这些影响,有人主张在有机化合物的风险评估中使用通用有机碳 - 水分配系数是不合理的,并且生物修复终点可以基于自由溶解浓度而不是沉积物/土壤中的总浓度来评估。